CN101117327B - Preparation method of aminocaprolactam - Google Patents
Preparation method of aminocaprolactam Download PDFInfo
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- CN101117327B CN101117327B CN2006100890371A CN200610089037A CN101117327B CN 101117327 B CN101117327 B CN 101117327B CN 2006100890371 A CN2006100890371 A CN 2006100890371A CN 200610089037 A CN200610089037 A CN 200610089037A CN 101117327 B CN101117327 B CN 101117327B
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- diacetyl oxide
- oxime
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- acetate
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Abstract
The invention discloses a preparation process for caprolactam which is characterized in that the acetic anhydride acts as the catalyzer to make a Beckmann rearrangement reaction of cyclohexanone oxime in ionic liquid homogeneous system , then the orgainic solvent is used to extract the ionic liquid and fully transfer the cyclohexanone oxime and the catalyzer into the organic solvent, finally the separation of the cyclohexanone oxime and the catalyzer is realized by the extraction to the solvent.
Description
Technical field
The present invention relates to a kind of preparation method of Organic Chemicals, prepare the method for hexanolactam more specifically to a kind of cyclohexanone-oxime through the Beckmann rearrangement reaction.
Background technology
Hexanolactam is a kind of important Organic Chemicals of widespread use, and about in the world 90% hexanolactam is prepared by the Beckmann rearrangement reaction by cyclohexanone-oxime.Traditional B eckmann rearrangement reaction process is: adopt oleum to make cyclohexanone-oxime form vitriolic hexanolactam salt, for the high yield that obtains hexanolactam need add excessive nicotinic acid, use the ammoniacal liquor neutralise mixt then, obtain sulphur ammonium and hexanolactam.In the typical industry rearrangement process, the transformation efficiency of cyclohexanone-oxime is almost 100%, is 99% to the selectivity of hexanolactam, produces 1.3-1.8kg sulphur ammonium/kg oxime (or 1.0-1.3mol oxime).This traditional technology uses oleum to be catalyzer and solvent, meeting severe corrosion equipment, harm environment, and consume the sulfuric acid and the ammonia of high value, the sulphur ammonium of a large amount of low values of by-product has increased production cost.Therefore the Beckmann rearrangement novel process of the no sulphur ammonium by-product of exploitation meets the Green Chemistry developing direction, is the improved target of preparing process of caprolactam.
Begin one's study from later 1960s and not use the improved rearrangement technology of oleum, comprise vapor phase rearrangement and liquid phase rearrangement technology.In recent years, Sumitomo company is obtaining bigger progress aspect the vapor phase rearrangement research, but vapor phase rearrangement technology is unsuitable for existing installation is carried out technological transformation; Liquid phase rearrangement technology has the reaction conditions gentleness, to equipment requirements advantages of higher not, come into one's own all the time, and obtain some achievements in research.
Inventa company has developed and has avoided the ammoniacal liquor neutral to reset technology (GB1029201): in the catalyst system that anhydrous acetic acid, diacetyl oxide and sulfonic acid type ion exchange resin are formed, cyclohexanone-oxime generation rearrangement reaction, suitable temperature of reaction is 107-120 ℃, the hexanolactam that generates combines with the sulfo group of ion exchange resin, then ion exchange resin is separated from the rearrangement system, obtain hexanolactam with the water treatment ion exchange resin that is lower than 5 ℃ again, the productive rate of hexanolactam reaches 95.5%.
In addition, Sumitomo company is at US5, and with alkylating reagent and N, dinethylformamide is made the liquid phase rearrangement catalyst system of solvent composition cyclohexanone-oxime in 225,547, and the cyclohexanone-oxime transformation efficiency is 100%, the hexanolactam selectivity is 99.8%; Dong Li company opens among flat 9-227509 and the flat 9-227510 of Te Kai the spy and adopts N, and dinethylformamide is a solvent, forms catalyst system with HCl and hydroxyl phosphorus trichloride, and the cyclohexanone-oxime transformation efficiency can reach 100%, the selectivity and the yield of hexanolactam can reach 95%; DSM N. V. is at US5, and 571,913 and EP0,639, use the cation exchange resin as catalyst of sulfo group benzene ring structure among the 565A1, hexanoyl imido grpup-O-sulfonic acid is made cocatalyst, and the hexanolactam yield is 100%, and the amount of vitriol by product is lower than 5%.
In recent years, ionic liquid is subjected to the great attention of academia and industry member as a kind of new catalytic material and green solvent.(petrochemical complex 2001,30 (2) 91-92) adopts butyl-pyridinium a tetrafluoro borate ([bupy] BF to Deng Youquan
4) and PCl
5Form catalyst system, the transformation efficiency of cyclohexanone-oxime and the selectivity of hexanolactam all approach 100%.
Though the selectivity of the transformation efficiency of cyclohexanone-oxime and hexanolactam is higher in the partial monopoly, because economy and technology, the catalytic liquid phase rearrangement technology of non-oleum fails to realize industrialization so far.
At present, the subject matter that exploitation liquid phase Beckmann rearrangement technology faces is: diacetyl oxide of (1) Inventa company and acetic acid catalysis rearrangement technology make spent ion exchange resin fractionation by adsorption hexanolactam, and treatment capacity is less; (2) in the ionic liquid homogeneous system or in ionic liquid/organic solvent two-phase system, with P contained compound (P
2O
5, PCl
3, PCl
5Or POCl
3) for catalyzer carries out rearrangement reaction, all generate and the very strong complex compound of P contained compound bonding force, and be difficult to from ionic liquid, isolate the hexanolactam of unbound state, ionic liquid and catalyzer recycle difficulty; (3) ammoniacal liquor neutralization procedure meeting by-product sulphur ammonium or other ammonium salts after rearrangement reaction finishes, and cause catalyzer can not or to be difficult for recycling; (4) the part catalyzer is (as P contained compound or SO
3Deng) can harm environment and health of human body.
Summary of the invention
The objective of the invention is not have sulphur ammonium by-product and reset the problems referred to above that technology faces at present exploitation, propose a kind of in the ionic liquid homogeneous system, adopt the Beckmann rearrangement reaction of diacetyl oxide catalysis of pimelinketone oxime to prepare hexanolactam, by the novel process of solvent extraction and separation catalyzer and hexanolactam, realize recycling of no sulphur ammonium by-product and ionic liquid and catalyzer then.
The preparation method of hexanolactam provided by the invention is characterized in that comprising the steps:
(1) under the rearrangement reaction condition, the ionic liquid solution of (a) cyclohexanone-oxime or cyclohexanone-oxime is contacted with ion liquid homogeneous phase ionic liquid with (b) diacetyl oxide carry out rearrangement reaction, obtain containing the ionic liquid solution of crude caprolactam, diacetyl oxide and acetate;
(2) with the ionic liquid solution of organic solvent extraction (1), obtain containing the organic solution of crude caprolactam, diacetyl oxide and acetate, ionic liquid recycles;
(3) organic solution of water extraction (2), acquisition contains the water of crude caprolactam, diacetyl oxide and acetate, and organic solvent recycles;
(4) with the water of extraction agent extraction (3), make separating of crude caprolactam and diacetyl oxide, acetate, crude caprolactam enters FF, and diacetyl oxide and acetate recycle after being processed into diacetyl oxide.
The described ionic liquid of the inventive method is dimerous by positively charged ion and negatively charged ion, and it deposits phase as carrying of catalyzer in reaction system.The ionic liquid that present method adopted both can be hydrophilic, also can be hydrophobic.
The cationic moiety of said hydrophilic ionic-liquid and hydrophobic ionic liquid is identical, can be selected from alkyl imidazole positively charged ion (C
3H
0-4N
2R
1-5 +, i.e. 2-5 the alkyl substituent that can have on the 1-5 position carbon of imidazole ring), alkyl pyridine positively charged ion (C
5H
5NR
+), quaternary ammonium salt cationic (R
1R
2R
3R
4N
+), season phosphonium salt positively charged ion (R
1R
2R
3R
4P
+), and above-mentioned cationic derivative or with one of similar organic cation of above-mentioned cationic structural.Wherein R, R
1, R
2, R
3, R
4, R
5For containing the alkyl of carbon number 1-12.
The anionicsite of hydrophilic ionic-liquid is selected from BF
4 -, Cl
-, Br
-, I
-, NO
2 -, NO
3 -, SO
4 2-, HSO
4 -, CF
3COO
-, (CN)
2N
-, CF
3SO
3 -, ClO
4 -Or C
4F
9SO
3 -Deng one of negatively charged ion.The anionicsite of hydrophobic ionic liquid is selected from PF
6 -Or (CF
3SO
2)
2N
-Deng one of negatively charged ion.
In the method provided by the invention, employed catalyzer is a diacetyl oxide, and the part diacetyl oxide is converted into acetate in reaction process.
The volumetric concentration of diacetyl oxide is 1%-60%, preferred 10%-30% in the ionic liquid.
In the method provided by the invention, Beckmann rearrangement reaction temperature is 30-150 ℃, preferred 50-100 ℃.
The cyclohexanone-oxime that adds catalyst system in the inventive method is the liquid or solid-state pure cyclohexanone-oxime that is below or above the rearrangement reaction system temperature, or is dissolved in the cyclohexanone-oxime solution in the ionic liquid.As use cyclohexanone-oxime solution, then its suitable concentration is 0.10-4.0mol/L, preferred 1.5-2.5mol/L.
The cyclohexanone-oxime mole dosage is 1 with the ratio of diacetyl oxide mole dosage in the inventive method: (1-3), preferred 1: (1.5-2.5).
Method provided by the invention can adopt intermittent feeding, discharge method or continuously feeding, discharge method operation.The rearrangement reaction time is 0.02-1.0 hour, preferred 0.05-0.2 hour when adopting the intermittent mode operation; When adopting the continuous mode operation is 0.01-300 second.
Adopt the organic solvent extraction ionic liquid solution in the inventive method, by multi-stage solvent extraction or continuous countercurrent extraction hexanolactam (CPL), diacetyl oxide and acetate are transferred in the organic solvent fully, ionic liquid recycles.
In the inventive method said organic solvent be immiscible with used ionic liquid, can form two-phase with the latter, CPL had the organic solvent of certain solubility.
The suitable organic solvent that is adopted among the present invention has benzene,toluene,xylene, trimethylbenzene, propyl carbinol, n-hexyl alcohol, n-Octanol, ether, n-butyl ether, ethyl acetate, butylacetate, pentyl acetate, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride, chlorobutane etc.
Adopting the purpose of water extraction organic solution in the inventive method is that CPL, diacetyl oxide and acetate are all transferred to water, above-mentioned several material is easier to be dissolved in the water, can make these several materials transfer to water fully by multi-stage solvent extraction or continuous countercurrent extraction, the raffinate organic solvent recycles after handling.Under comparatively high temps, the diacetyl oxide in the aqueous solution could be converted into acetate fully, therefore still has diacetyl oxide in the aqueous solution.
The extraction agent of said CPL of being used for and diacetyl oxide, separated from acetic acid can be neutral phosphorus-based extractant or organic extractant in the inventive method.
Neutral phosphorus-based extractant in the inventive method comprises tributyl phosphate (TBP), trioctyl phosphate, tricresyl phosphate alkane ester, TRPO (TRPO) etc., can directly use above-mentioned neutral phosphorus-based extractant, or they are dissolved in the organic solvent as extraction agent, the two-phase system that extraction agent and water are formed is realized separating of CPL and diacetyl oxide, acetate by complexing solvent extraction principle.The organic solvent of dissolving neutral phosphorus-based extractant mainly is alkane and aromatic hydrocarbons, and as normal hexane, normal heptane, octane-iso, sherwood oil, benzene,toluene,xylene etc., the volumetric concentration of neutral phosphorus-based extractant is 10%-99.9%.
Also can realize the separating of CPL and diacetyl oxide, acetate with the two-phase system that water is formed by physical solvent extraction principle as the organic extractant of extraction agent (as trichloromethane etc.) in the inventive method.
Method provided by the invention has following advantage:
(1) efficient, highly selective realizes that the Beckmann rearrangement reaction of cyclohexanone-oxime prepares hexanolactam, as with [bmim] BF
4Among the embodiment 1 of homogeneous system, the transformation efficiency of cyclohexanone-oxime is up to 100%, and the selectivity of hexanolactam is up to 97.9%, and the overall selectivity of hexanolactam and pimelinketone is up to 98.4%.
(2) after rearrangement reaction finishes, obtain the hexanolactam of unbound state, without the ammoniacal liquor neutralization procedure, no sulphur ammonium by-product.
(3) can realize recycling of ionic liquid, catalyzer and extraction agent.
(4) rearrangement reaction can be carried out in very wide temperature and time scope, realizes the control to speed of reaction easily.
Embodiment
The invention will be further described below in conjunction with embodiment, but content not thereby limiting the invention.
Embodiment 1
Present embodiment explanation the present invention can be at [bmim] BF
4Implement in the homogeneous system.
At first in the 100ml triangular flask, add wetting ability [bmim] BF
4Ionic liquid 40ml and diacetyl oxide 15ml, the ionic liquid solution of acquisition diacetyl oxide adds [bmim] BF then in the 250ml round-bottomed flask
4Ionic liquid 50ml and cyclohexanone-oxime 10 grams, 70 ℃ of oil bath temperature controls, magnetic agitation drips the ionic liquid solution of the diacetyl oxide for preparing again, and reaction 10min obtains to contain the ionic liquid solution of CPL, diacetyl oxide and acetate.With toluene extracting ionic liquid solution, the relative content of each material in the gas chromatographic analysis toluene solution.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 97.9%, and the overall selectivity of hexanolactam and pimelinketone is 98.4%.
In the 250ml Erlenmeyer flask, add toluene and each 50ml of ionic liquid solution, at room temperature magnetic agitation is 60 minutes, static phase-splitting in the separating funnel, ionic liquid recycles.The gas chromatographic analysis toluene solution is determined the amount of CPL in the toluene with marker method.The result shows that 20% CPL transfers to the toluene phase, by multi-stage solvent extraction CPL, diacetyl oxide, acetate is transferred in the toluene fully easily.
In the 250ml Erlenmeyer flask, add each 40ml of toluene solution of entry, at room temperature magnetic agitation is 30 minutes, static phase-splitting in the separating funnel.With the water that chloroform extraction obtains, gas chromatographic analysis chloroform soln, determine the amount of CPL in the trichloromethane with marker method.The result shows that 68% CPL transfers to water, by multi-stage solvent extraction CPL, diacetyl oxide, acetate is transferred in the water fully easily.
Tributyl phosphate (TBP) can pass through complexometric extraction principle extracting and separating CPL and acetate effectively from the aqueous solution.At first in 100ml tool plug triangular flask, add the aqueous solution 30ml that contains 10% (V/V) acetate and 10% (W/V) CPL, add TBP30ml then, magnetic agitation 1.5h at room temperature, static phase-splitting in the separating funnel, the gas chromatographic analysis TBP and the aqueous solution are determined the content of each material in the solution with marker method.The result shows that 95.4% CPL is retained in water, and promptly CPL is 0.0482 at the partition ratio of TBP/ water two-phase system; 36.9% acetate is retained in water, and promptly acetate is 1.71 at the partition ratio of this two-phase system.CPL and acetate are 35.5 at the separation factor of this two-phase system, can effectively realize separating of CPL and acetate.
Embodiment 2
Present embodiment explanation the present invention can be at hydrophobicity [bmim] [PF
6] middle enforcement.
At first in the 50ml test tube, add [bmim] [PF
6] ionic liquid 25ml and cyclohexanone-oxime 1.0g, be warming up to 120 ℃, obtain the ionic liquid solution of cyclohexanone-oxime, in the 100ml round-bottomed flask, add [bmim] [PF then
6] ionic liquid 30ml and diacetyl oxide 1.5ml, obtain the ionic liquid solution of diacetyl oxide, 120 ℃ of oil bath temperature controls, magnetic agitation drips the ionic liquid solution of the cyclohexanone-oxime for preparing, reaction 3min again.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 85.4%.
Embodiment 3
Present embodiment explanation the present invention can be at hydrophobicity [C
12Mim] [(CF
3SO
2)
2N] implement in the homogeneous system.
At first in the 50ml test tube, add wetting ability [C
12Mim] [(CF
3SO
2)
2N] ionic liquid 15ml and diacetyl oxide 15ml, the ionic liquid solution of acquisition diacetyl oxide.In the 100ml round-bottomed flask, add [C
12Mim] [(CF
3SO
2)
2N] ionic liquid 15ml and cyclohexanone-oxime 10 grams, 30 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 60min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 91.6%.
Embodiment 4
Present embodiment explanation the present invention can be at [bupy] [NO
2] (wherein [bupy]
+Be 1-butyl-3-picoline positively charged ion) implement in the homogeneous system.
At first in the 50ml test tube, add wetting ability [bupy] [NO
2] ionic liquid 20ml and diacetyl oxide 15ml, the ionic liquid solution of acquisition diacetyl oxide.In the 100ml round-bottomed flask, add [bupy] [NO
2] ionic liquid 25ml and cyclohexanone-oxime 4.0 grams, 80 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 15min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 94.2%.
Embodiment 5
Present embodiment explanation the present invention can be at wetting ability [C
3 1C
2 3C
4] [NO
3] ([C wherein
3 1C
2 3C
4Im]
+Be 1-propyl group-3-ethyl-4-methylimidazole positively charged ion) implement in the homogeneous system.
At first in the 50ml test tube, add [C
3 1C
2 3C
4] [NO
3] 20ml and diacetyl oxide 7.5ml, obtain the diacetyl oxide ionic liquid solution.In the 100ml round-bottomed flask, add [C
3 1C
2 3C
4] [NO
3] ionic liquid 25ml and cyclohexanone-oxime 5.0 grams, 90 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 20min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 95.3%.
Embodiment 6
Present embodiment explanation the present invention can be at [bmim] [(CN)
2N] implement in the homogeneous system.
At first in the 50ml test tube, add wetting ability [bmim] [(CN)
2N] ionic liquid 20ml and diacetyl oxide 10ml, the ionic liquid solution of acquisition diacetyl oxide.In the 100ml round-bottomed flask, add [bmim] [(CN)
2N] ionic liquid 30ml and cyclohexanone-oxime 5.0 grams, 90 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 30min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 96.6%.
Embodiment 7
Present embodiment explanation the present invention can be at [(C
2H
5)
4N] implement in the Br homogeneous system.
At first in the 50ml test tube, add wetting ability [(C
2H
5)
4N] Br ionic liquid 20ml and diacetyl oxide 7.5ml, the ionic liquid solution of acquisition diacetyl oxide.In the 100ml round-bottomed flask, add [(C
2H
5)
4N] Br ionic liquid 30ml and cyclohexanone-oxime 5.0 grams, 60 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 15min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 93.5%.
Embodiment 8
Present embodiment explanation the present invention can be at [(C
4H
9)
4P] [HSO
4] implement in the homogeneous system.
At first in the 50ml test tube, add wetting ability [(C
4H
9)
4P] [HSO
4] ionic liquid 20ml and diacetyl oxide 7.5ml, the ionic liquid solution of acquisition diacetyl oxide.In the 100ml round-bottomed flask, add [(C
4H
9)
4P] [HSO
4] ionic liquid 30ml and cyclohexanone-oxime 5.0 grams, 90 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 15min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 96.8%.
Embodiment 9
Present embodiment explanation the present invention can be at wetting ability [bmim] [CF
3COO] implement in the homogeneous system.
At first in the 50ml test tube, add [bmim] [CF
3COO] ionic liquid 20ml and diacetyl oxide 7.5ml, the ionic liquid solution of acquisition diacetyl oxide.In the 100ml round-bottomed flask, add [bmim] [CF
3COO] ionic liquid 30ml and cyclohexanone-oxime 5.0 grams, 90 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 15min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 92.9%.
Embodiment 10
Present embodiment explanation the present invention can be at [bmim] [ClO
4] implement in the homogeneous system.
At first in the 50ml test tube, add wetting ability [bmim] [ClO
4] ionic liquid 20ml and diacetyl oxide 7.5ml, the ionic liquid solution of acquisition diacetyl oxide.In the 100ml round-bottomed flask, add [bmim] [ClO
4] ionic liquid 30ml and cyclohexanone-oxime 5.0 grams, 90 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 15min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 94.7%.
Embodiment 11
Present embodiment explanation the present invention can be at [bmim] [SO
4] implement in the homogeneous system.
At first in the 50ml test tube, add wetting ability [bmim] [SO
4] ionic liquid 20ml and diacetyl oxide 7.5ml, the ionic liquid solution of acquisition diacetyl oxide.In the 100ml round-bottomed flask, add [bmim] [SO
4] ionic liquid 30ml and cyclohexanone-oxime 5.0 grams, 100 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 15min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 95.5%.
Embodiment 12
Present embodiment explanation the present invention can be at [bmim] [CF
3SO
3] implement in the homogeneous system.
At first in the 50ml test tube, add wetting ability [bmim] [CF
3SO
3] ionic liquid 20ml and diacetyl oxide 7.5ml, the ionic liquid solution of acquisition diacetyl oxide.In the 100ml round-bottomed flask, add [bmim] [CF
3SO
3] ionic liquid 30ml and cyclohexanone-oxime 5.0 grams, 90 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 10min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 96.2%.
Embodiment 13
Present embodiment explanation the present invention can be at wetting ability [bmim] [C
4F
9SO
3] implement in the homogeneous system.
At first in the 50ml test tube, add [bmim] [C
4F
9SO
3] ionic liquid 20ml and diacetyl oxide 7.5ml, the ionic liquid solution of acquisition diacetyl oxide.In the 100ml round-bottomed flask, add [bmim] [C
4F
9SO
3] ionic liquid 30ml and cyclohexanone-oxime 5.0 grams, 100 ℃ of oil bath temperature controls, magnetic agitation, the ionic liquid solution of the diacetyl oxide that dropping prepares, reaction 20min.The transformation efficiency of cyclohexanone-oxime is 100.0%, and the selectivity of hexanolactam is 93.3%.
Embodiment 14
Present embodiment explanation tributyl phosphate (TBP)/sherwood oil (b.p.:90-120 ℃) solution can extract principle extracting and separating CPL and acetate effectively from the aqueous solution by complexing solvent.
At first, in 100ml tool plug triangular flask, add the aqueous solution 30ml that contains 10% (V/V) acetate and 10%CPL (W/V), add 75%TBP/ petroleum ether solution 30ml then, magnetic agitation 1.5h at room temperature, static phase-splitting in the separating funnel, the gas chromatographic analysis organic phase and the aqueous solution are determined the content of each material in the solution with marker method.The result shows that 95.6% CPL is retained in water, and promptly CPL is 0.0460 at the partition ratio of this profit two-phase system; 46.0% acetate is retained in water, and promptly acetate is 1.174 at the partition ratio of this profit two-phase system.CPL and acetate are 25.5 at the separation factor of TBP-sherwood oil/water two-phase system, easily effectively realize separating of CPL and acetate by multi-stage solvent extraction or continuous countercurrent extraction.
Embodiment 15
The present embodiment explanation can use trichloromethane to go out CPL by physical solvent extraction principle extracting and separating from the aqueous solution, and acetate is retained in water, thereby effectively realizes separating of CPL and acetate.
At first, in 100ml tool plug triangular flask, add the aqueous solution 30ml that contains 10% (V/V) acetate and 10%CPL (W/V), add trichloromethane 30ml then, magnetic agitation 1.5h at room temperature, static phase-splitting in the separating funnel, the gas chromatographic analysis trichloromethane mutually and the aqueous solution is determined the content of each material in the solution with marker method.The result shows that 88.6% CPL enters the trichloromethane phase, and promptly CPL is 7.77 at the partition ratio of trichloromethane/aqueous systems; 69.5% acetate is retained in water, and promptly acetate is 0.439 at the partition ratio of trichloromethane/aqueous systems.CPL and the acetate separation factor in trichloromethane/aqueous systems is up to 17.7, effectively realizes separating of CPL and acetate by multi-stage solvent extraction or continuous countercurrent extraction easily.
Claims (18)
1. the preparation method of a hexanolactam is characterized in that comprising the steps:
(1) under the rearrangement reaction condition, the ionic liquid solution of (a) cyclohexanone-oxime or cyclohexanone-oxime is contacted with ion liquid homogeneous phase ionic liquid with (b) diacetyl oxide carry out rearrangement reaction, obtain containing the ionic liquid solution of crude caprolactam, diacetyl oxide and acetate;
(2) with the ionic liquid solution of organic solvent extraction (1), obtain containing the organic solution of crude caprolactam, diacetyl oxide and acetate, ionic liquid recycles;
(3) organic solution of water extraction (2), acquisition contains the water of crude caprolactam, diacetyl oxide and acetate, and organic solvent recycles;
(4) with the water of extraction agent extraction (3), make separating of crude caprolactam and diacetyl oxide, acetate, crude caprolactam enters FF, and diacetyl oxide and acetate recycle after being processed into diacetyl oxide.
2. according to the method for claim 1, it is characterized in that in the said ionic liquid that cationic moiety is selected from alkyl imidazole positively charged ion, alkyl pyridine positively charged ion, quaternary ammonium salt cationic, season phosphonium salt positively charged ion.
3. according to the method for claim 1, it is characterized in that said ionic liquid is a hydrophilic ionic-liquid, anionicsite is selected from BF
4 -, Cl
-, Br
-, I
-, NO
2 -, NO
3 -, SO
4 2-, HSO
4 -, CF
3COO
-, (CN)
2N
-, CF
3SO
3 -, ClO
4 -Or C
4F
9SO
3 -One of.
4. according to the method for claim 1, it is characterized in that said ionic liquid is a hydrophobic ionic liquid, anionicsite is selected from PF
6 -Or (CF
3SO
2)
2N
-
5. according to the method for claim 1, the ionic liquid solution concentration that it is characterized in that (a) said cyclohexanone-oxime in the step (1) is 0.10-4.0mol/L.
6. according to the method for claim 5, the ionic liquid solution concentration that it is characterized in that said cyclohexanone-oxime is 1.5-2.5mol/L.
7. according to the method for claim 1, it is characterized in that in the step (1) that the volumetric concentration of diacetyl oxide is 1%-60% in (b) said diacetyl oxide and ion liquid homogeneous phase ionic liquid.
8. according to the method for claim 7, the volumetric concentration that it is characterized in that said diacetyl oxide is 10%-30%.
9. according to the method for claim 1, it is characterized in that the said rearrangement reaction temperature of step (1) is 30-150 ℃.
10. according to the method for claim 9, it is characterized in that the rearrangement reaction temperature is 50-100 ℃.
11., it is characterized in that the middle cyclohexanone-oxime of step (1) and the ratio of diacetyl oxide mole dosage are 1: 1-3 according to the method for claim 1.
12., it is characterized in that the said cyclohexanone-oxime and the ratio of diacetyl oxide mole dosage are 1: 1.5-2.5 according to the method for claim 11.
13., it is characterized in that the said rearrangement reaction of step (1) adopts intermittently charging and discharging mode or continuous charging and discharging mode to operate according to the method for claim 1.
14. according to the method for claim 13, it is characterized in that adopting charging and discharging at intermittence mode to operate, the reaction times is 0.02-1.0 hour.
15. according to the method for claim 13, it is characterized in that adopting the continuous charging and discharging mode to operate, the reaction times is 0.01-300 second.
16. according to the method for claim 1, it is characterized in that the said organic solvent of step (2) be immiscible with used ionic liquid, can form two-phase with the latter, hexanolactam had the organic solvent of certain solubility.
17. method according to claim 16, it is characterized in that said organic solvent is selected from benzene,toluene,xylene, trimethylbenzene, propyl carbinol, n-hexyl alcohol, n-Octanol, ether, n-butyl ether, ethyl acetate, butylacetate, pentyl acetate, trichloromethane, tetracol phenixin, 1, one or more in 2-ethylene dichloride and the chlorobutane.
18. according to the method for claim 1, it is characterized in that the said extraction agent of step (4) is a neutral phosphorus-based extractant, volumetric concentration is 10%-99.9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102001999A (en) * | 2010-11-02 | 2011-04-06 | 河北工业大学 | Process for directly synthesizing caprolactam from cyclohexanone and hydroxylamine |
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| US7812191B2 (en) | 2008-05-07 | 2010-10-12 | Lyondell Chemical Technology, L.P. | Removing hydrocarbon impurities from acetic acid by ionic liquid extraction |
| CN101684076B (en) * | 2008-09-25 | 2013-04-17 | 中国石油化学工业开发股份有限公司 | Method for preparing amide |
| CN102311386B (en) * | 2010-07-02 | 2013-05-15 | 天华化工机械及自动化研究设计院有限公司 | Caprolactam suspension filtering and washing method |
| CN103288735B (en) * | 2012-02-29 | 2015-03-04 | 北京安耐吉能源工程技术有限公司 | Catalyst system for Beckmann rearrangement and method for preparing caprolactam thereof |
| CN103288734B (en) * | 2012-02-29 | 2015-04-29 | 北京安耐吉能源工程技术有限公司 | Catalyst system for Beckmann rearrangement and method for preparing caprolactam thereof |
| CN102675176B (en) * | 2012-05-31 | 2016-12-14 | 中国天辰工程有限公司 | A kind of be raw material production caprolactam with high pure benzene method |
| CN102863385B (en) * | 2012-10-09 | 2014-01-01 | 清华大学 | Method for directly synthesizing caprolactam through cyclohexanone |
| CN104356039B (en) * | 2014-11-10 | 2017-02-15 | 河北美邦工程科技有限公司 | Preparation process of caprolactam |
| CN109970646B (en) * | 2018-12-28 | 2024-01-12 | 南京科技职业学院 | Cyclohexanone oxime transposition process flow |
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